TWI225969B - Photosensitive resin composition, patterning method, and electronic components - Google Patents

Abstract

A photosensitive resin composition comprising an aromatic polyimide precursor, wherein a 10 mum thick layer of precursor has light transmittance at a wavelength of 365 nm of at least 1% and a 10 mum thick polyimide film made from the resin composition by imidation ring closure and deposited on a silicon substrate results in a residual stress of at most 25 MPa. The composition can be patterned through i-line exposure followed by development with alkaline solutions, and can be imidized into low-stress polyimide patterns. Electronic components having the polyimide patterns have high reliability.

Description

1225969 A7 B7 V. Description of the invention (1) Field of invention (please read the note on the back? Matters before filling out this page) The present invention relates to a photosensitive resin composition, a method for patterning the composition, and using the same Electronic component made of photosensitive resin composition. 2 · Description of related technologies Recently, in the semiconductor industry, organic substances having good heat resistance, such as polyimide resins, have been used as interlayer insulation materials instead of conventional inorganic materials because of their good characteristics. The patterning of semiconductor integrated circuits and printed circuits requires many complicated steps, such as forming an anti-contact film on the surface of the substrate, removing unnecessary parts of the film by selective exposure and leaving aside at a predetermined position, and cleaning The surface of the substrate thus treated. Therefore, it is desirable to develop a heat-resistant photosensitive material for use as a photoresist, which can be directly used as an insulating layer after being patterned through exposure and development. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Heat-resistant photosensitive materials have proposed the use of, for example, photosensitive polyimide and cyclic polybutadiene as basic polymers. In particular, photosensitive polyimide is worthy of attention because of its good heat resistance and its ability to remove impurities (such as water, solvents, photopolymers of polymers, photoinitiators, sensitizers, etc.). A system comprising a polyimide precursor and a dichromate has been proposed in such a photosensitive polyimide (refer to JP_B 49-17374). The advantages of the proposed system are useful light sensitivity and good film formation capabilities, but the disadvantages are poor storage stability and the presence of chromium ions in the polyimide. Because of this disadvantage, such a system cannot be put into practical use. In order to solve these problems, a hybrid polyimide precursor was proposed. The paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) 1 311836 1225969 A7

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (2) Method of compound and photosensitive compound (for example, refer to JP_A M l⑽, etc.) and a combination of polyimide precursor and compound with photosensitive group.

Method, so the photosensitive group is introduced into the precursor of polyimide (refer to JP_A 56-24343, 60-100143, etc.) 〇 Because of the ancient, soil > et also become the sensitivity Polyimide precursors are mainly derived from aromatic monomers. The aromatic monomers have good heat resistance and good mechanical properties, but due to the light absorption of the polyimide precursors, the UV light transmission is low. As a result, the photochemical reaction in the exposed area of the polyimide film is often insufficient (ie, the sensitivity is low). As a result, the use of the aforementioned photosensitive polyfluorene imide precursor for patterning is often problematic because the side view of the pattern formed by the low sensitivity of the polyfluorine imide film and the resolution are not good. With the increase of the degree of integration of semiconductors in the industry, the design rules of semiconductor devices have become more and more sophisticated, and semiconductor devices have been required to have a higher degree of analysis. When manufacturing semiconductor devices, a 1 ·· 1 projector (called a projection lens) and a reduced projector (called a stepper) are used, for example, to replace the conventional contact / near-end projector with parallel light. Subtle circuit pattern. For the stepper, monochromatic light such as high-powered chirped light from an ultrahigh-pressure mercury lamp or an excimer laser beam can be used. The so-called g-line stepper is the most common stepper. This stepper uses g-line visible light (wavelength 436 nm) from an ultra-high pressure mercury lamp. However, in order to satisfy the requirements of more recent finer working rules, the wavelength of the light applied to the stepper needs to be shortened. In this case, use an i-line stepper (wavelength: 365 nm) instead of a g-line stepper (wavelength: 436 nm). But as mentioned above, it is designed for contact / proximity projector, projection lens and g-line (please read the precautions on the back before filling this page) | Installation -------- Order ------- --Line · This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 2 311836 1225969 A7 B7 V. Description of the invention 〇) (Please read the precautions on the back before filling this page) Stepper The conventional light-sensitive polyfluorene imide basic polymer has a poor linear light transmittance, and the i-ray transmittance through the polymer is close to zero. Therefore, the use of a linear stepper to pattern the conventional photosensitive polyimide produces poor patterns. The LOC (lead-on-wafer) high-density package system used to fabricate semiconductor devices requires a thick polyimide film as a surface protection. In the case of thick polyimide, the problem of poor light transmission is worsened. It is highly desirable that the photosensitive polyimide has a high soil transmittance and can be patterned into a good pattern using an i-line stepper. In this regard, it has been reported that the introduction of certain substituents into the aromatic ring of the photosensitive polyimide backbone can effectively improve the 1-line transmittance of polyimide (refer to JP_A 8-337652, etc.). The diameter of a broken wafer used as a substrate for a semiconductor device becomes larger. The result of the increase in straight length caused another problem. The difference in thermal expansion coefficient between the polyimide film and the underlying silicon wafer caused by the Shixi wafer coated with a polyimide film with a surface protection effect was better than the previous song. More. In this case, it is intended to find a photosensitive polyimide having a coefficient of thermal expansion smaller than that of the conventional polyimide. Polyimide with rigid rod-like molecular structure usually has low thermal expansion. However, the typical polyimide i-rays with a rigid rod-shaped molecular structure are printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Therefore the ability to photo-pattern this type of polyimide is generally low. SUMMARY OF THE INVENTION According to the foregoing object, the present invention provides an aromatic polyfluorene imide precursor having a high i-line transmittance, which can be amidated to a polymer having a low thermal expansion coefficient and a low mechanical stress on a silicon wafer. Fluorene imine resin, and a photosensitive resin composition containing a precursor. This composition also has advantages such as good heat resistance, high sensitivity, and high resolution. This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 3 311836 1225969 A7 B7 V. Description of the invention (4) The present invention also provides a photosensitive resin composition that can be developed using an aqueous alkaline solution. Aqueous alkaline solutions are more environmentally friendly than solvent-based imaging agents. (Please read the notes on the back before filling this page) The present invention also provides a patterning method for obtaining a polyimide pattern with a good side view. This method uses the aforementioned photosensitive resin composition. Due to the high i-line transmittance and high sensitivity, the polyimide precursor of the composition can be easily processed through 1-line exposure to obtain a high-resolution pattern. The polyimide film formed after the imidization has good heat resistance and low mechanical stress on silicon wafers. Another advantage of the patterning method according to the present invention is that an environmentally friendly aqueous test solution can be used for the development of the method. The present invention further provides a reliable electronic component having a high-resolution polyimide pattern. The polyimide pattern formed in electronic components has good side views, high heat resistance, and minimal residual stress. In particular, the present invention provides the following preferred embodiments: Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (1) A photosensitive resin composition comprising an aromatic polyimide precursor, wherein the precursor layer is 10 micrometers thick A polyimide film having a light transmittance of at least 1% at 365 nanometers and a polyimide film made of a polyimide composition and deposited on a silicon substrate via closure of the imidium ring and obtained on a silicon substrate is available Residual stress up to 25 million Baska. (2) The photosensitive resin composition of (1), wherein the light transmittance at a wavelength of 365 nm of a thin film of 10 µm thick made of an aromatic polyimide precursor is at least 5%. (3) A photosensitive resin composition comprising an aromatic polyimide precursor 'wherein the aromatic polyimide precursor has a repeating structure of the general formula ⑴ This paper applies Chinese National Standard (CNS) A4 Specifications (210 X 297 public love) 4 311836 1225969 A7 V. Description of the invention (5) Unit: > < x, > < >-or one < >-where A and B represent trivalent or A tetravalent aromatic group; and X & γ, respectively, represents a photosensitive resin composition of at least one diamidine (4) (3) that is not bonded to A or B, and has a structural formula of () The aromatic polyfluorene imide precursor has a repeating structural unit of the general formula (II) ...

< D each

I (II) (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, where A and B represent tetravalent aromatic radicals, respectively; X and γ respectively indicate that they are not related to A or B A divalent group bonded together; Z represents at least one divalent aromatic group; R1 and R2 each represent a hydroxyl group or a monovalent organic group, respectively. (5) The photosensitive resin composition of (1) or (2), wherein the aromatic polyfluorene imide precursor is the composition of (3) or (4). (6) The photosensitive resin composition of (4), wherein Ri or r2 of the formula (Π) is a monovalent organic group having a photosensitive group. (7) The photosensitive resin composition of (4), wherein R1 or R2 of formula (II) is a group of the following formula: -0 n + hr4r5-r6 -0-R6 or -NH-R6 wherein R4 and R5 are each Respectively represents a hydrocarbon group and R6 represents a monovalent organic group. Wood paper scale is applicable to China National Standard (CNS) A4 (210 X 297 mm) 311836 I --- I ---- Order--I ------ line. 1225969 Staff Consumption of Intellectual Property Bureau, Ministry of Economic Affairs A7 B7 printed by the cooperative V. Description of the photosensitive resin composition of (6) (8) (7), in which R6 is a group containing a carbon-carbon unsaturated double bond. (9) The photosensitive resin composition of (7), wherein R1 or R2 of the formula (Π) is a group of the following formula: -On + hr4r5-r6 In the formula, R4 and R5 each represent a hydrocarbon group and R6 represents a carbon-containing group. Carbon unsaturated double bond is a monovalent organic group. (10) The photosensitive resin composition of (7), wherein Ri or R2 in the formula (η) is a group of the following formula: _0_R6, where R6 represents a monovalent organic group. (11) The photosensitive resin composition according to any one of (1) to (10), wherein the aromatic polyfluorene imide precursor is soluble in an aqueous alkaline solution. (12) The photosensitive resin composition of (10), wherein z in the formula (η) is a group having a carboxyl group or a phenolic group. (13) The photosensitive resin composition of (10), wherein z in the formula (π) is a base of the general formula (III):

In the formula, Z ′ represents a single bond, 0, CH2, S, or S〇2; R11 to R18 each represent Η, COOH, OH, an alkyl group having 1 to 10 carbon atoms, and fluorine containing 10 to 10 carbon atoms. Burnt-based 'fluoroalkoxy group containing 1 to 10 carbon atoms This paper is sized for the Chinese National Standard (CNS) A4 (210 X 297 mm) 311836 ---, --- ^ ----- · pack- ------- Order --------- Line (Please read the precautions on the back before filling this page)

1225969 A7 V. Description of the Invention (7) or a halogen atom, and wherein at least one of the feet 11 to feet 1 S is COOH or OH. (14) The photosensitive resin composition according to any one of (3) to (13), wherein χ and Υ respectively represent a carbonyl group, an oxy group, a thio group, a sulfinyl sulfenyl group, and a sulfonyl group, containing 1 to 5 The carbon atom is optionally substituted with an alkylene, an imine, a silyl or any combination of these. (15) The photosensitive resin composition of (14), wherein χ and γ each represent an oxy group, a thio group, a sulfofluorenyl group, a selective methylene group or a silyl group. (16) The photosensitive resin composition according to (15), wherein χ is a selectively substituted methylene group and Y is an oxy group. (17) The photosensitive resin composition according to any one of (3) to (16), wherein both A and B are benzene rings. (18) The photosensitive resin composition of any one of (1) to (17), which further contains a photopolymerization initiator and has negative photosensitive characteristics. (19) The photosensitive resin composition of any one of (17) to (17) further contains a compound capable of generating an acid from light, and has a positive photosensitive property. (20) —A method for forming a pattern, comprising applying the photosensitive resin composition of any one of (丨) to (19) to a substrate, drying and exposing the composition, developing the composition, and This composition is heated to form a pattern layer. (2 1) The patterning method of (20), wherein the linear radiation is used as a light source in the exposure step. (22) (2〇) or (21) patterning method, wherein the substrate is a paper with a diameter of up to 1 paper size applicable to Chinese national standards (CNSM4 specifications coffee x Qiao public hair) 311836 7 1225969 A7 B7-five, Description of the invention (8) Silicon wafers as small as 12 inches. (Please read the precautions on the back before filling out this page) (23) The electronic component has a patterned layer according to the method of any one of (20) to (22). (24) The electronic component of (23) is used for a semiconductor device, and the patterned layer is used for a surface protective film or an interlayer insulating film. Further objects, features and advantages of the present invention will be apparent from the detailed description of preferred embodiments hereinafter, taken in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS FIGS. 1A to 1E show a method of manufacturing a semiconductor device without a multilayer interconnection structure. Figures 2A to 2C schematically illustrate the use of negative and positive photosensitive resin compositions. Detailed description of the invention The functions of the negative and positive photosensitive resin compositions printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs are illustrated in Figures 2A to 2C. Fig. 2A shows that the ultraviolet light 24 is projected onto the photosensitive resin composition layer 22 through a photomask 20. Light 24 exposes part 26, leaving part wound 2 5 unexposed. In the negative photosensitive resin composition, the exposed portion is crosslinked or polymerized and then hardened, and the unexposed portion 25 is removed by a developer to remove the pattern of the exposed portion 26, as illustrated in FIG. 2C. In the positive photosensitive resin composition, the exposed portion 26 is made more soluble by the action of light. Thus, the exposed portion 26 is removed by the developer, leaving a pattern of the unexposed portion 25. As will be discussed later, the photosensitive resin composition of the present invention includes a negative type composition and a positive type composition. Before the photosensitive resin composition of the present invention contains aromatic polyimide, the paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) 8 311836 1225969 B7 V. Description of the invention (9) The fluorene imine precursor contains repeating units with aromatic rings at least = in them. In particular, the precursors include aromatic polyamino acids; aromatic polyamino acids, which are derived from aromatic polyamino acids via some or all of the acetic acid groups; and aromatic polyamino acids Amine 'is derived from aromatic polyamines via partial or full amination of the carboxyl group of the aromatic polyamines. The aromatic polyfluorene imide precursor used in the present invention is preferably one in which the light transmittance of the thin film having a thickness of 1 m is transmitted through the precursor at a wavelength of 365 nm, preferably at least 3%, Better at least, and still better at least 10%. If the light transmittance is less than 1%, it is difficult to obtain a photosensitive resin composition which can be patterned into a high-resolution pattern with a good side view. A particularly good light transmittance is 10% to 80%. Polyimide precursors can be formed by applying a solution of a polyimide precursor to a solvent onto a substrate and then drying. The light transmittance through a polyimide film at a wavelength of 365 nanometers can be measured using a spectrophotometer (such as Hitachi υ_3410 from Hitachi). It is also better printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The aromatic polyfluorene imide precursor of the present invention is closed by a polyimide ring to form a polyfluorine film, and when deposited on a silicon wafer, it has a surplus The stress is not more than 25 million Baska. If the residual stress is more than 1 million basca, the disadvantage of the polyimide film made of the precursor-containing composition of the present invention is that when formed on a silicon wafer or when used on a silicon wafer, the silicon crystal The circle is warped and the residual stress inside the silicon wafer is large. More preferably, the residual stress according to the present invention is 0 to 20 million Baska. The residual stress of the polyimide film is measured at room temperature of 25 ° C, for example, using a film stress meter (such as the model Tencor FLX-2320). This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 public copy) 9 311836 1225969 A7 V. Description of the invention (10) The aromatic polyimide of the photosensitive resin composition according to the present invention is preferred The precursor has the above formula ⑴ repeating unit (staircase structure) in the repeating unit (please read the precautions on the back before filling in this page). In principle, the polyimide precursor with the structural formula described above satisfies the above requirements for the film at 365 millimeters. Microwavelength light transmittance and residual stress requirements of the resulting polyimide film. The repeating unit of human-made aromatic polyimide precursors usually indicates that the instruction contains the following units: containing acetic acid residues derived from tetra-acid dianhydride and the like derived from a starting character used as a precursor, and derived from It is also used as an amine residue of a diamine of another starting compound. In the above reaction plan, the structural unit of the formula may be a part of a carboxylic acid residue or a dicarboxylic acid residue or may be a part of a diamine residue or a monoamine residue. Particularly preferred is an aromatic polyfluorene imine precursor having a structural unit of formula (I), or more preferably a repeating unit of formula (11) because the precursor has a high rod-like structure after the imidization, and the reason The reason is that the residual stress of the polyimide is low. Formulas ⑴ and ’each represent a trivalent or tetravalent aromatic radical (but printed by Formula (II) as a tetravalent aromatic radical) by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The aromatic group referred to here is a group having an aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, a pyridine ring, a furan ring, a quinoline ring, and the like. Two or more aromatic rings may be bonded to each other via any bond to obtain an aromatic group. However, it is preferred that the aromatic group contains an aromatic ring. The aromatic ring of this group may be substituted: preferably the X and Y diyl groups are bonded to A and 8 at the ortho or para position of the aromatic ring, for example, as shown in the following formula: Private paper scales apply Chinese national standards ( CNS) A4 specification (210 X 297 mm) 311836 1225969 V. Description of the invention (Π)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. It is better than the polyimide precursors with repeating units of formula (II), which are bonded to the rebel or counterposition of the repeating units. ^ Examples of ortho-positions ⑴ and ⑼ and B and (B) located in the aromatic ring are described later ^ and ^ (referred to as "tri-group" groups) include paracyclic aromatic groups such as anthracene_2,3,6_ Three groups: 芴 2,3,6 one group, etc., double jade clothing aromatic groups, such as Tsai Sanji, Tsai M, 5.triyl, quinine '3> triyl, etc .; monocyclic aromatic groups such as benzene], 2,4_triyl, pyridine-2,3,5_triyl, furan_2,3, 'triyl, etc., all may have a substituent. Tetravalent radicals (referred to herein as "tetrayl" radicals) include paracyclic aromatic radicals: such as anthracene _2,3,6,7-tetrayl, _2,3,6,7_tetrayl, etc. ; Bicyclic aromatic groups such as naphthalene-2,3,6,7 · tetrayl, naphthalene ten 4,5,8-tetrayl, perylene-2,3,6,7-tetrayl, etc .; monocyclic aromatic groups For example, benzene · tetrayl, tetrazine_2,3,5, tetramethyl, furan-2,3,4,5-tetrayl, etc., all of which may optionally have a substituent. Among them, a monocyclic aromatic group optionally having a substituent is preferable; a phenyltetrayl group is selectively substituted; and a benzene β1,2,4,5-tetrayl group is more preferably substituted. X and Υ each represent at least one divalent group which is not conjugated to A or B, respectively. Special divalent radicals include carbonyl, oxy, thio, sulfenyl (i.e. a divalent radical containing fluorenyl), fluorenyl (i.e. a divalent radical containing Li), containing 1 to 5 carbon atoms Selective substitution of the alkylene group, selective substitution of the imino group, and selection of any combination of these groups. These groups make 'preferred' to be oxy, thio, hydrazone, and optionally substitute sub- ▼ groups (please read the note on the back? Matters before filling out this page) Μ -------- ^ --------- This paper size applies to China National Standard (CNS) A4 (210 X 297) 11 311836 1225969 A7 ----- B7____ 5. Description of the invention (l2) and optional replacement extension The reason for the silyl group is that the polyimide driver containing any of the foregoing groups has good i-ray transmittance and heat resistance. The substituents which the A, B, X and Y groups have include a monovalent substituent and a divalent substituent. Special substituents include selectively branched alkyl groups containing 丨 to 10 carbon atoms; halogen atoms containing 1 to 10 carbon atoms substituted selective branched alkyl groups (wherein halogen atoms include gas, fluorine, iodine, and bromine); Alkenyl groups of 1 to 10 carbon atoms, alkynyl groups of 1 to 10 carbon atoms; aromatic hydrocarbon groups of 6 to 20 carbon atoms such as phenyl, T group, etc .; Alkoxy; tooth atom containing 1 to 10 carbon atoms substituted alkoxy (where _atom includes gas, fluorine, iodine and bromine); cyano; halogen atom (such as gas, fluorine, iodine and bromine); elephant group , Amine group, azide group, thiol group; trialkyl group, each of which contains 1 to 5 carbon atoms; alkylene group containing 2 to 5 carbon atoms; carbonyl group; 'Oxy, sulfenyl; fluorenyl; fluorenyl; dialkylene sulphydryl, wherein each alkyl group contains 1 to 5 carbon atoms; and combinations of the foregoing. Preferred substituents are alkyl groups containing 1 to 5 carbon atoms, halogen-substituted alkyl groups containing 1 to 5 carbon atoms, alkoxy groups containing 1 to 5 carbon atoms, and alkyl groups containing 1 to 5 carbon atoms. Halogen atoms replace alkoxy groups, aromatic hydrocarbon groups, and elongation groups containing 2 or 3 carbon atoms. Preferred examples of the structural unit including A, B, X, and Y are described later. (Please read the precautions on the reverse side before filling out this page) I Sang -------- Order ----- I --- Line · Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Consumer Cooperatives This paper is suitable for China National Standard (CNS) A4 Specification (210 X 297 mm) 12 311836 1225969 A7 B7 V. Description of Invention (l3 Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs

---, ---: ----- • Installation -------- Order --------- Line #L (Please read the precautions on the back before filling this page) This Paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 13 311836 1225969 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

A7 V. Description of the invention (M) In formula (II), the Z group is a optionally substituted divalent aromatic group. Usually this is the starting diamine residue, which is derived from the diamine by removing two amine groups. Specific examples of this group include p-phenylene, m-phenylene, 4,4, -biphenylene, 4,4, -triphenylene, 4,4'-oxyphenylene, 4,4, Methylene phenylene, 4,4, diphenyl sulfate, 4,4'-sulfonyl phenyl diphenyl, and 4,4, carbonyl phenyl diphenyl, all have substituents. Preferred groups are the selective substitution of p-phenylene, 4,4, -biphenylene and 4,4'-triphenylene because of the polyfluorene imide prepared from precursors containing any of the foregoing groups. The reason for the small residual stress. Substituents for the aforementioned groups include those described in the text for the A, B, X and γ groups. Preferred substituents are also as described above. The aromatic polyfluorene imide precursor preferably used in the present invention is soluble in an aqueous test solution. The photosensitive resin composition of the present invention, which contains such an alkali-soluble precursor, can be developed using an aqueous alkali solution, and the adverse effect of the aqueous alkali solution on the environment is minimized. A preferred method for preparing an aromatic polyfluorene imide precursor having the structural unit of formula (I) which is soluble in an aqueous alkaline solution is to produce a precursor having a repeating unit of formula (II), where Z is a tacky group or an actinide Jingji. From the viewpoint of the i-line transmittance of the precursor and the low stress and heat resistance of the polyimide made from the precursor, and in order to develop in a positive image mode, Z of the preferred formula (II) is a structural formula (III) Group: (III) In the formula, Z represents a single bond, 〇, CH2, S or S02; R " to R18 are each divided into paper sizes that apply the Chinese National Standard (CNS) A4 (210 X 297 mm) 311836 · Install -------- Order --------- (Please read the precautions on the back before filling this page) 1225969 A7 B7 V. Description of the invention (15) (Please read the back Please fill in this page again) Do not indicate H, COOH, OH, alkyl group with 1 to 10 carbon atoms, fluoroalkyl group with i to 10 carbon atoms, fluoroalkoxy group with 1 to 10 carbon atoms Or at least one of a halogen atom and Rn to R18 is COH or OH. Preferred examples of the group of formula (ΠΙ) are as follows:

In formula (Π), R1 and R2 each represent a hydroxyl group or a monovalent organic group, respectively. The preferred categories and ratios of R1 and R2 in formula (II) are changed depending on whether the expected composition is positive or negative. Examples of monovalent organic radicals of R1 and R2 are as follows: printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs _ON + HR4R5-R6 -0_R6 or -NH-R6 where R4 and R5 each represent a hydrocarbon group, and r6 represents a Valent organic radical. For a negative composition, the R6 group is preferably a photosensitive group. Photosensitive groups contain carbon-carbon unsaturated double bonds. Examples of groups containing carbon_carbon unsaturated double bonds are: -ON + HR4R5_R7 -〇-R7 or the size of this paper applies Chinese National Standard (CNS) A4 (210 X 297 public love) 15 311836 1225969 A7 B7 Ministry of Economy Printed by the Intellectual Property Bureau's Consumer Cooperatives 5. Description of the invention 〇6) -NH-R7 where 'R4 and R5 each represent a hydrocarbon group, and R7 represents a monovalent organic group containing a carbon-carbon unsaturated double bond. Preferably, R4 and R5 are each a hydrocarbon group containing i to 5 carbon atoms. Also preferred is a monovalent organic group containing a carbon-carbon unsaturated double bond of R7, for example, a propylene alkyloxy group or a methacrylic alkyloxy group, wherein the alkyl group contains from 1 to 10 carbon atoms. As for the negative photosensitive resin composition, it is desirable (but at least partially) that the repeating unit of the carboxylic acid residue branching the aromatic polyfluorene imide precursor composed of 20 to 100 mol% is preferably (formula ( II) The neutralized R2 group) is a monovalent organic group having a carbon-carbon unsaturated double bond. For the positive photosensitive resin composition, a carboxyl group and a _〇_ R6 or -NH-R6 monovalent organic group are preferred (where R6 is a monovalent organic group containing no carbon-carbon unsaturated double bond). , Such as hydrocarbyl, etc.). The hydrocarbyl group includes, for example, an alkyl group having 1 to 6 carbon atoms, a phenyl group, a benzyl group and the like. In the positive photosensitive resin composition, the branching chain of the rebel residue (which is a group of R1 and R2 in the formula (II)) of the repeating unit constituting the aromatic polyimide precursor is the aforementioned monovalent organic group. The diamine residue of the preferred precursor contains an alkali developable group (for example, a carboxyl group, a phenolic hydroxyl group, etc.) such as a group of formula (III). Aromatic polyfluorene imide precursors having structural repeat units of formula (I) further contain any additional polyfluorine imide precursor repeat units, except for structural formula (J) and any repeat units of polyimide. In this case, the ratio of the repeating unit having the formula (I) to the total repeating units constituting the precursor | {Column & is not particularly defined, but is preferably controlled to the paper size of the polyimide precursor itself Applicable to China National Standard (CNS) A4 specification ⑵G x 297 (issued) (Please read the precautions on the back before filling out this page) -Installation -------- Order --------- Line · 16 311836 1225969 (IV) A7 B7 V. Description of the invention (I7) The transmittance of 365 nanometers and the derivative derived from the precursor via the amidation reaction < polyimide's heat resistance and low thermal expansion can meet the requirements defined here . It is particularly desirable that the ratio of the repeating unit having the structural formula (I) to all repeating units is in the range of 10 to 100 mole%, more preferably 50 to 100 mole%. The molecular weight of the aromatic polyfluorene imide precursor used in the present invention is not particularly defined, but its weight average molecular weight is preferably in the range of 10,000 to 200,000. Molecular weight was determined by gel permeation chromatography based on polystyrene standards. The aromatic polyfluorene imide precursor used in the present invention can be prepared from an acid component containing a tetracarboxylic dianhydride of the general formula (IV): cx: x > 〇 〇 wherein a, b, x and γ have such as The same definition of formula (I), or its bamboo organism; and an aromatic diamine (herein, Z is defined as formula (II)) with an amine component including H2N-Z-NH2, and optionally one can provide R1 and R2 Residue-to-precursor compounds, which are prepared by reacting these ingredients via various methods. For the precursors of the present invention, repeating units having the structural formula (I) are indispensable. However, the effect of the present invention is not impeded, and the tetrabasic acid dianhydride or the derivative thereof having the structural formula of the formula (i) may not be combined. The tetracarboxylic dianhydride without the formula (I) is preferably a rigid rod with Γ% (read the precautions on the back and fill in this page first) i I n H ϋ H ϋ un ϋ n — — — — — II ϋ II 一口 TI. ^ 1 ϋ n I ϋ II-Printed and printed scales of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs are applicable to China National Standard (CNS) A4 (210 X 297 mm 17 311836 K25969 A7 V. Description of the invention (find) dianhydride with a structure, such as pyromellitic acid, 3 3, 5, 4 _ bis-tetracarboxylic acid and other dianhydrides. Further preferred Taiwan red paper magnetic 'preferred-anhydrides include For example, the following dianhydrides of various aromatic tetracarboxylic acids: for example, thiodiphthalic acid 'oxydiphthalic acid; 3 3,4 4, dibasic tetracarboxylic acid ~ from naphthalene tetrahydroacid ^ from Tsai tetrametaconic acid' ^ octa Tetra-acid '2,3,5,6__tetrapyrene' 3 4 9 1 () _ DiCai Jingjingtetrakidic acid, canthamidio diacid, m-triphenyl_3,3 ', 4, 4, _tetratonic acid, p-tribenzyl-3,3,, 4,4'_ four-money, mm hexafluoro_2 21 (2 3 seven, 4_ dilephenyl) propane, 2,2- Wu (2,3_ or 3,4_ Dibubenji C) C, 22_ Wu (4 '-(2,3_ or 3,4 · Diphenylphenoxy) phenyl Propane, 1, l, l, 3,3,3_hexagas_2,2 Dai {4χ2,3- or 3,4-diphenylphenoxy) phenyl} propane '1,3_dai (3, 4_Jun Benz Magic Book '1,4-Wu (3,4-Bent phenoxy) stupid, 4,4, _Wu (34 phenoxy) diphenyl shout, 4,4 _ 贰 (3,4 · Carboxyphenoxy) biphenyl, and other aromatic tetracarboxylic dianhydrides of general formula (v):

(V) 〇 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) where R 'and R' 'are the same or different and each represents 1 to 10 Hydrocarbon group per atom, and s represents 0 or any integer. One or more of these edges can be used individually or in combination. As for the tetraphosphonic acid dianhydride derivative, for example, tetra gingeric acid, tetracarboxylic hydrazone gas, and the like are included. The amount of the tetra-acid dianhydride of the formula (IV) used in the reaction is preferably 10 to 100 mol% of the total tetracarboxylic acid used therein. If the amount is less than 10 mol 0 / 〇, the i-ray transmittance through the generated polyfluorene imide precursor will decrease. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 18 311836 I 25969 A7

V. Description of the invention (19) The square monoamine is any of the known diamines, including, for example, p- (or m-) benzidine diamine, 2,4_ (or 2,5-, 2,6-, or 3) , 5-) diaminomethylbenzyl- 跄 it + 2,5_ (or 2,6-) monoamino_p-xylene, 2,4- (or 2,5- or 4,6 ·) diamine Phenyl-m-monobenzyl, 3,5- (or 3,6-) diamino-o-toluene, 2,4-diamino = mono # 3,6_-diamino mesitylene, benzidine, o- Toluidine, u τ aniline, 4,4,-monoaminotriphenyl, 1,5_ (or 2,6-) diaminonaphthalene, 2,7-diamine and its derivatives, 4,4,- (Or 5 2,4'- or 2,2 '-) diaminodiphenyl_, 4 4 ,, +, 4 _ (or 3,4,-, J, 3 _, 2, 4, or 2 , 2 '-) diaminodiphenylmethane, 4,4,-(or 3 4,3,3,3'-'2,4'- or 2,2'-) diaminodiphenyl mill, 4,4,-(or 3,4, _, j 3,2,4, or 2,2 '-) diaminodiphenyl sulfide, 4 4, 〆5, a book ▼ _diamine, U, l, 3,3,3-hexafluoro_2,2_2 (4-aminophenyl) propane, 2,2, _ 贰 (trifluoromethyl) benzidine, 2,2,-贰 ( Trifluoromethoxy) benzidine, etc. One or more of these groups can be used alone or in combination. -Any of the following groups can be introduced into precursors to make them soluble in water-based solutions: Employees' cooperation with the Intellectual Property Bureau of the Ministry of Economic Affairs

Alkali-soluble aromatic polyfluorene imide precursors containing any of the aforementioned diamine residues can be developed with alkali after exposure, and the material is safer for personal use "/ :! Pass the Chinese National Standard (CNS) A4 specification (⑽χ 297 公 楚) 19 311836 ----------- install -------- order --------- line (please read the precautions on the back first) (Fill in this page) 1225969 A7 ----------- §z _________ 5. The working environment of invention description (2〇) and the advantages of simple processing waste liquid etc. (Please read the precautions on the back before filling in this page ) In order to make polyfluorinated acid for the precursor of polyfluoreneimide (wherein R1 and R2 are both hydroxyl groups), tetracarboxylic dianhydride can be reacted with monoamine through organic ring-opening addition polymerization; In this example, the ratio of tetrametamic acid dianhydride to diamine is preferably in the range of 0.7 / 1 to 1 / 0.7 mole ratio. The reaction is typically performed in an organic solvent. The organic solvent used is preferably Proton-inert polar solvents' that completely dissolve the polyfluorene imide precursor formed include, for example, N-methyl-2-0-pyrrolidinium, N, N-dimethylacetamide, N, N-methylmethyl Amine, n, N-dimethyl-2-imidazolidinone, dimethyl sulfene, tetramethyl urea, trimethylamine hexamethylphosphonic acid, butyrolactone, etc. Printed by the Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs In addition to polar aprotic solvents, nationals, esters, lactones, ethers, toothed hydrocarbons, hydrocarbons, etc. can be used. Among the useful solvents include acetone, diethyl ketone, methyl ethyl methyl Ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethyl acetate, monoethyl carbonate, δ-valerolactone, ethyl bond, Dimethyl glycol mystery, Diethylene glycol dimethyl ether 'tetrahydrofuran, dioxane, gas-form, digas methane, 1,2--gas ethane', 1,4-digas butane, trigas ethane Gas benzene, o-digas benzene, hexane, heptane, octane, benzene, toluene, xylene, etc. One or more of these organic solvents can be used alone or in combination. It is used to make polyfluorene of formula (II) Amine precursors, in which R1 and R2 each have a photosensitive group bonded to it ionicly. Polyamine amino acid can be mixed with acrylic compounds containing an amine group. . Acrylic compounds with amine groups to be used for ion-bonding photosensitive groups include, for example, N, N-dimethylaminoethyl methacrylate, N, N methacrylic acid. This paper is in accordance with Chinese National Standards (CNS ) A4 specification (21 × X 297 public love) 20 311836 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1225969 A7 ^ ___ B7___ One or five, the description of the invention (21) Diethylaminoethyl 'methylpropionate n, n-dimethylaminopropyl 'N, N-diethylaminopropyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate , Acrylic acid N, N-dimethylaminopropyl acetate, acrylic acid-diethylaminopropylacetate 'N, N_difylaminoacrylamide, N, N-dimethylaminoethyl Acrylamide and so on. One or more of these groups may be used alone or in combination. The amount of the acrylic compound is preferably 1 to 200 parts by weight, and more preferably 5 to 150 parts by weight, based on 100 parts by weight of the polyamic acid mixed with it. If the amount is less than 1 part by weight, the sensitivity of the formed polyimide precursor is not good. However, if the amount is more than 200 parts by weight, the heat resistance and mechanical properties of the resulting polyfluorene imide film will be poor. In order to manufacture polyfluorinated esters of polyfluorinated imine precursors, tetracarboxylic dianhydride is first reacted with an alcohol compound to obtain a tetracarboxylic acid diester, and then the diester is reacted with sulfinic gas to obtain a tetracarboxylic diester. Bidentate. The resulting dihalide is then dissolved in an organic solvent and reacted with a diamine in an organic solvent containing a dehydronanide agent such as pyridine. The reaction method is to add the former dropwise to a solution of the latter in a solvent. The resulting reaction mixture is poured into a poor solvent such as water, and the precipitate formed and dehydrated are removed by filtration. As for the alcohol compound used in the photosensitive resin-containing polyamino acid S for the negative photosensitive resin composition, the unsaturated alcohol compound is preferably an unsaturated alcohol compound including, for example, methyl methacrylate, methyl methacrylate, Hydroxyethyl acrylate, ethyl methacrylate, propyl acrylic acid, methacrylic acid propyl, hydroxybutyl acrylate 'hydroxybutyl methacrylate, and the like. Particularly preferred are hydroxyalkyl acrylates and methacrylic acids in which the alkyl bond portion contains 1 to 10 carbon atoms .-------- Order --------- line (please first Read the notes on the reverse side and fill out this page) This paper size applies to the Chinese National Standard (CNS) A4 (210 X 297 mm) 21 311836 1225969 A7 V. Description of the invention (22) Ester. The base is not used for the positive photosensitive resin composition without photosensitivity: known, the alcohol compound used is preferably a saturated alcohol compound Γ to; 1 saturated alcohol compound preferably contains 1 ^ carbon Atom-based alcohols include, for example, methanol 'ethanol, n-propanol, isopropanol, n-butanol, first butanol, third butanol, lidin ^% isobutanol, pentanol, 2-pentyl alcohol Alcohol, 3-pentanol, isoamyl alcohol '1-hexanol, hexanol, 1 p ^^ hexanol, hexanol, and the like. One or more of these alcohols may be used alone or in combination. When the tetracarboxylic diesters are installed, the ratio of the tetracarboxylic anhydride to the alcohol compound is preferably between 1/2 and 1 / 2.5 mole ratio, but the best & 1/2 mole ratio. The comparison of tetramellitic dianhydride is preferably 1 / 0.001 to 1/3 mole ratio, and more preferably 1 / 0.005 to 1/2 mole ratio. The reaction temperature is preferably from 10 to 60, and the reaction time is preferably from 3 to 24 hours. Known methods can be used for the next step in the production of tetracarboxylic diester dianhydrides. For example, sulfenylpyridine gas is added dropwise to a solution in which a tetracarboxylic acid diester is dissolved in an organic solvent, and reacted with the diester. The comparison of the tetracarboxylic diester to sulfenyl is preferably 1/1 · 1 to 1 / 2.5 mole ratio, and more preferably ln 5 to 1/22 mole ratio. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The reaction temperature is preferably -20 ° C to 40 ° C, and the reaction time is preferably j to 10 hours. This paper size applies to China National Standard (CNS) A4 specifications (210: in the next step, the tetracarboxylic diester diester produced previously is dissolved in an organic solvent, and it is present with a diamine in a dehydrogenating agent such as pyridine, etc. For this reaction, a dioxide solution is added dropwise to the diamine and dehydrogenated to obtain a polyamidate from a solution of a chemical agent in an organic solvent. After the reaction, the reaction mixture is poured into a poor solvent such as water, etc. The obtained sinker is obtained by filtration and dehydration 311836 1225969 A7 V. Description of the invention (23 (Please read the note on the back? Matters before filling out this page) to obtain the desired polyamidate. The total amount of diamine used is tetracarboxylic The comparison of the acid diester bidentate is preferably from 0.6 / 1 to 1/06 mole ratio, and more preferably from 0.7 / 1 to 1 / 0.7 mole ratio. The reaction temperature is preferably 20. To 40.0, and the reaction time is preferably 1 to 10 hours. The comparison of the dehydrohalogenating agent to the four acid diesters is preferably 18/1 to 2 2/1 mole ratio, and more The preferred ratio is from 1-9 / 1 to 莫 · 8 / ΐ to 2.2 / 1 mole ratio, and more preferably from 9/1 to 2 · ιπ mole ratio. The polyamidoamines used for the imine precursor can be used in the same way as the polyaminoesters described above, but using monoamines instead of alcohol compounds. Monoamine compounds include, for example, methylamine, Ethylamine, n-propylamine, isopropylamine, n-butylamine, second butylamine, third butylamine 'isobutylamine, 1-pentylamine, 2-pentylamine, 3_ Amylamine, isoamylamine, 1-hexylamine, 2-hexylamine, 3-hexylamine, morpholine, aniline, fluorenylamine 'and various unsaturated amines such as acrylic acid aminoalkyl esters, Aminoalkyl methacrylates, etc. The photosensitive resin composition of the present invention printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is characterized by containing any of the foregoing polyimide precursors. Various methods can be used for manufacturing A photosensitive composition. For example, as in the foregoing specific embodiment, a method of introducing a carbon-carbon unsaturated double bond group into the branch of the polyimide precursor itself can be used to produce a polyfluorene having a photocrosslinkable structure. An imine precursor can make a composition containing the precursor photosensitive. The method is to add a compound containing a carbon-carbon unsaturated bond and an amine group (for example, amine acrylates) to the composition, and it can be ionic bonded to the polyimide precursor of the composition. It can also be used This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 23 311836 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1225969 A7 ____B7_____ V. Description of the invention (24) The method addition contains one or more Carbon-carbon unsaturated double bond reactive monomer to the composition, so that the composition becomes photosensitive. In addition, a method can be used to add a photosensitizer such as a photoacid generator, a photobase generator, etc. to the composition in. These methods are known in the industry. In principle, in the negative-type photosensitive resin composition of the present invention, the 5′-imine halide according to the present invention itself contains a carbon-carbon unsaturated double bond, otherwise a compound containing a carbon-carbon unsaturated double bond is added. Into the composition. The preferred composition further contains a photopolymerization initiator together with these components. Photopolymerization initiators include, for example, Michler (S) ketone, benzoin methyl ether 'benzoin ethyl ether, benzoin isopropyl ether, 2-third butyl anthracene ratio, 2-ethyl anthracene, 4 4,4- (diethylamino) benzophenone, acetophenone, benzophenone, thia anthracene, 2,2-dimethoxy-2-phenylacetophenone, hydroxycyclohexylphenyl Methanone, 2-methyl- [ren (methylthio) phenyl; | _2_morpholinyl_acetone dibenzidine, diphenyl disulfide, phenanthrene, 2-isopropylthioanthracene Ketone, riboflavin tetrabutyrate, 2,6 · fluorene (p-diethylaminobenzaldehyde) _4_methyl-4-acylcyclohexyl_, N_ethyl-^ (p-aerophenyl) Glycine, n-phenyldiethanolamine, 2- (o-ethoxycarbonyl) oximediphenylpropanedione, p-phenyl_2oxo-ethoxycarbonyl) oximepropanone-1, 3 , 3,4,4-Tetrakis (Third-butylperoxycarbonyl) dibenzoyl, 3,3_carbonylpyrene (7_diethylaminocoumarin), 贰 (cyclopentadienyl) · 贰[2,6-difluoro · 3_ (pyridyl) phenyl] titanium and a variety of azide compounds such as hydrazone azide of the following structural formula: ----------- pack ------ --Order --------- (Please read the back of the note Pou? Matters to fill out this page) this fiscal dumping paper size 243,118,361,225,969

V. Description of the invention (25)

(Please read the note on the back? Matters before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, and the photopolymerization initiator content of the product is relative to the weight of the polyimide of the compound The precursor is preferably from 0.01 to 30 parts by weight | to ratio, and more {from 0.05 to 10 parts by weight. If the content is less than 〇1, ⑺ 蕙, then the sensitivity of the product is not good. However, if the content is more than 30 parts by weight, the mechanical properties of the t-polyimide film become poor. The negative photosensitive resin composition of the present invention may contain 6 or more kinds of addition polymerizable compounds having carbon-carbon unsaturated double bonds. Additives such as Diethylene Glycol Dipropylene Acid Mill, Triethylene Glycol Dipropylene Blend :: Glycol Diacrylate, Diethylene Glycol Dimethacrylate, Dimethacrylate, Tetraethylene Glycol Alcohol dimethacrylate, trimethylolpropane as diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trifyl acrylate, J, Renbutanediol diacrylate, 1,6-hexanediol diacrylate;!, Butanediol dimethymethane Paper size applies to Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 25 311836 1225969 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 --------£ 1__ -------__ V. Description of the invention (26) Bing & since the day '1, 6_Jiji Alcohol-Methyl Propionate, Pentaerythritol Tripropionate 'Pentaerythritol Tetraacrylate, Pentaerythritol Trimethacrylate, Pentaerythritol Tetramethacrylate, Styrene, Divinylbenzene, Menthyl Toluene, 4 -Vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylic acid Esters, 1,3-propenyloxy-2-hydroxypropane, 1,3-methacrylic acid 2-hydroxypropane, methylene-propionamine, n, n_: methacrylamide, N- Hydroxymethacrylamide and the like. One or more of these groups can be used individually or in combination. The content of the addition polymerizable compound in the composition is from i to 200 parts by weight based on 100 parts by weight of the aromatic polyfluorene imide precursor. If the content is less than 1 part by weight, the solubility and / or sensitivity of the composition to the developer will be poor. However, if the content is more than 200 parts by weight, the mechanical properties of the resulting polyfluorene imine thin film become poor. A radical polymerization inhibitor or a retarder may be added to the negative photosensitive resin composition of the present invention to improve the storage stability of the composition. Free-radical polymerization inhibitors or retarders include, for example, p-methoxyphenone, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiagen, m-phenylene, o-one, basic, right Diacylbenzene 'm-di wallylbenzene, phenanthrene g-Kun, N_phenyl_1_naphthylamine' N-phenyl-2-naphthylamine, cup ferr on, phenothiazine, 2,5 -toluene, tannic acid, p-benzylamine group, sub-group; g, stilbylamines and so on. One or more of them may be used alone or in combination. The amount of the radical polymerization inhibitor or the retarder of the composition is preferably from 0.001 to 30 parts by weight, and more preferably from 0.05 to the aromatic polyimide precursor of the composition by weight. To 10 parts by weight. If the content is less than ---- · ---: ----- · install -------- order --------- line # l · (Please read the note on the back first 咅? Please fill in this page again) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 26 311836 1225969 A7

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V. Description of Invention (28) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. In order to improve the adhesion of the hardened film of the composition to the substrate, the composition may additionally include any one of an organic stone compound, a chelate compound, and a stone-containing polyamic acid. Preferred organic silane compounds include, for example, γ-aminopropyltrimethoxysilanylaminoaminodiethoxyxanthine, ethylene triethoxyxanthine, γ-glycidyloxypropyldiethyl Oxygen oxalate, γ-methyl propyl oxypropyltrimethoxy oxalate, triethoxysilyl propyl ethyl carbamate, N_ (triethoxy oxalyl propyl) urea, etc. . Aluminum chelate compounds include, for example, Ethyl (ethylpyruvate), aluminum diisopropylate, and the like. The photosensitive resin composition of the present invention is applied to silicon wafer substrates, metal substrates, ceramic substrates, etc. by means of dip coating, spray coating, screen printing, spin coating, etc., and is heated and dried to remove most of the solvent. A non-stick film is formed on the substrate. The thickness of the formed film is not particularly limited, but in view of the circuit characteristics and the like of the device including the film, it is preferably 4 to 50 microns, more preferably 6 to 40 microns, and more preferably 10 to 40 microns, and more preferably It is 20 to 35 microns. Since the photosensitive resin composition of the present invention can form a polyimide film with low residual stress, it can be advantageously used for large-size wafers, such as silicon wafers having a diameter of 12 inches or more. The film of the composition is exposed to light or other electromagnetic radiation such as beta or gamma rays through a photomask having a predetermined pattern, and the unexposed or exposed areas of the film (depending on the negative or positive activity) are subsequently developed by using an appropriate developer. Like removal, a patterned film is thus obtained. The photosensitive resin composition of the present invention is advantageous for using i-wire stepping ----------- installation -------- order --------- line (please Please read the notes on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 28 311836 Π25969 A7 V. Description of the invention (29) (Please read the note on the back first? Matters Fill out this page again} for i-ray exposure, but the present invention is not limited to this purpose. In addition to f-ray exposure, the silk film of the present invention can also be used to step high waste lights, projection mirrors, and g-line. And any other projectors or light sources such as ultraviolet, visible X-rays, electron rays, etc. are processed using a contact / near-end projector. Developers include, for example, organic solvent developers (e.g., n, n-di Methylformamide, N, N • dimethylacetamide, N_methyl · 2_pyrrolidine, etc.) or mixed solvent imaging agents (such as lower alcohols, _, Water, aromatic hydrocarbons, etc.), and strong detection imaging agent. If the polyimide precursor of the composition can be dissolved in aqueous alkaline solution, An aqueous alkali solution can be used as a developer of the composition film. The aqueous alkali solution contains, for example, up to 5% by weight of any one of sodium hydroxide, potassium hydroxide, sodium silicate, tetramethyl hydroxide, and the like, and Preferred is an aqueous solution of 5 to 30% by weight. A more preferred developer is an aqueous solution containing tetramethylammonium hydroxide with a content of 15 to 3.0% by weight. The surfactant and other materials are printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and others. Additives may be added to the developer. The content of various additives (if any) relative to 100 parts by weight of the developer is preferably from 0.01 to 10 parts by weight, and more preferably from 0.1 to 5 parts by weight. After development, the processed film is selectively but preferably washed with water or a poor solvent, and then dehydrated at about 100t, so that the patterned film is stabilized. Then the patterned film is heated to obtain a low heat resistance. Stress relief pattern film. The heating temperature is preferably in the range of 150 to 50 ° C, and more preferably in the range of 200 to 400 ° C. If the heating temperature is lower than 15 ° rc, the mechanical film size of the resulting film is ¥ paper size Applicable to China Standard (CNS) A4 (210 X 297 mm) 29 311836 Π25969 A7 B7 V. Description of the invention (30) The properties and thermal characteristics are not good. If it is higher than 50 (rC, the mechanical properties and thermal characteristics of the thin sheet) It will also be poor due to thermal decomposition and / or crosslinking. (Please read the note on the back? Matters before filling out this page) The heating time is preferably 0.05 to 10 hours. If the heating time is shorter than 0.05 hours 'The mechanical properties and thermal characteristics of the obtained film are poor. If it is longer than 10 hours', the mechanical properties and thermal characteristics of the obtained film are also not good. The photosensitive resin composition of the present invention can be used in electronic components such as semiconductor devices, Multilayer interconnect boards, etc. In particular, the composition of the present invention can be used for forming a surface protection film and an interlayer insulating film in a semiconductor device, or for forming an interlayer insulating film in a multilayer interconnection board. The electronic component of the present invention is not particularly limited as long as it has a surface protective film or an interlayer insulating film made of such a composition, and may have various structures. An example of the manufacturing method of the electronic component of the present invention will be described later, in which the manufacturing of a semiconductor device is taken as an example. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Figures 1A to 1E show the manufacturing method of a semiconductor device with a multilayer interconnection structure. As shown, the semiconductor substrate 1 (such as a semiconductor substrate made of silicon, etc.) has a circuit element coated with a protective film 2 (such as silicon dioxide, etc.), except for a predetermined portion of the circuit element; and the first conductive layer 3 Formed on the exposed circuit element. The semiconductor substrate is coated with a thin film 4 (for example, a resin or the like) according to a spin coating method or the like (step in FIG. 1A) as an interlayer insulating film. Next, a phenol-phenol novolac resin or other equivalent photosensitive resin layer 5 is formed on the interlayer insulating film 4 by a spin coating method, and a window 6 A is formed through the window according to a known photolithography technique (step 1B). A predetermined portion of the interlayer insulating film 4 is exposed to the outside. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 30 311836 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Γ225969 A7 ____B7___ V. Description of the invention (31) Interlayer insulation film under each window 6 A 4 According to the dry etching method, a window 6B is formed by selective etching using vapors such as oxygen and carbon tetrafluoride. Next, the photosensitive resin layer 5 is completely removed by using an etching solution capable of etching only the photosensitive resin layer 5, but the first conductor layer 3 exposed to the outside through the window 6B is not etched (step in FIG. 1C). Next, a second conductor layer 7 is formed according to a known photolithography technique, which is completely electrically connected to the first conductor layer 3 (step in FIG. 1D). In order to form a multilayer interconnection structure having 3 or more layers, the steps are repeated for each layer. Next, a surface protection film 8 is formed (step in FIG. 1E). In the example, a surface protection film is formed according to a spin coating method, in which the photosensitive resin composition of the present invention is applied to a wafer and dried thereon. The film is then exposed through a reticle, which has a pattern of windows 6C formed with predetermined components. The subsequently exposed film was developed using an aqueous alkali solution to obtain a predetermined pattern, and the pattern was heated to produce a patterned resin film with stress relief. This resin film protects the conductor layer from contact with external stress α, α rays, and the like, and the semiconductor device thus manufactured has good reliability. In the example shown, the interlayer insulating film is also formed of the photosensitive resin composition of the present invention. Further details of the invention will be illustrated with reference to the following examples, but by no means intended to limit the scope of the invention. Production Examples 1 to 3: Diamine component of m-toluidine and N-methyl-2-Π-pyrrolidone (NMP) solvent were placed in a 100 ml flask equipped with a stirrer and a thermometer, and ----------- Install -------- Order --------- Line 411 ^ l · (Please read the note 3 on the back before filling this page) This The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 public love) 31 311836 1225969 A7 V. Description of the invention (32) (Please read the precautions on the back before filling this page) Hungry to dissolve. The obtained solution was added with the acid components shown in the following Table 丨 and stirred for 24 hours to obtain a viscous solution of the polyimide precursor. The solution was heated to a viscosity of 100 poise (poiseK solid content: 25% by weight). Thus, a polyfluorene imide precursor solution (PAAq to pAA-3) was obtained. Table 1 shows the results of using diamine knife, acid content, NMP content, and molecular weight of the obtained polyimide precursor. Emperor Makes You 丨 4: Printed in Table 1 by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, half of the N, N-dimethylacetamide (DMAc) solvent 'and 2 equivalents of 2-hydroxyethyl methacrylate The ester was placed in a 100 ml flask equipped with a stirrer and a thermometer. 22 equivalents of pyridine were added with stirring at room temperature. The mixture was further stirred at 60 to 7 ° C for 1 hour, then cooled to room temperature and allowed to stir overnight. The mixture was cooled to 0 ° C, and then 2 6 equivalents of sulfenylsulfonium gas were added dropwise with stirring. After returning to room temperature, the mixture was stirred A tritium solution was obtained in 2 hours. In addition, the diamine component of m-toluidine, the rest of DMAc and 2 equivalents of pyridine were placed in a 100 ml flask equipped with a stirrer and a thermometer, and dissolved at room temperature with stirring. , And then cooled to 0 ° C. When the resulting mixture was stirred, the previously prepared osmium chloride solution was added dropwise thereto, and the resulting mixture was further stirred at room temperature for 1 hour to obtain a polyfluorene imide precursor solution. This precursor was again exposed to ions. The precipitate was exchanged in water, and the obtained solid was washed with water and then dehydrated under vacuum to obtain a polyimide precursor (PAA-4). The diamine component, the acid component, the amount of DMAc, and the molecular weight of the obtained polyimide precursor are shown in the sheet Standards are applicable to China National Standard (CNS) A4 specifications mo X 297 mm 32 32311836 1225969 A7

V. Description of the invention (33) Table 1 Manufacturing Example 1 Ingredient i ~ (Amount) 11.46 g (25 mmol) Diamine component (amount) (25 mmol) Solvent (amount) NP 50.29 g Polyimide Precursor PAA-1 ~~ Weight average — good amount 108,000 Manufacturing Example 2 10 · 11 g (25 mmol, 5.31 g (25 mmol) NM 46.25 g PAA-2 113,000 Manufacturing Example 3 9.16 g (25 mmol) Moore) 5.31 grams (25 millimoles) NMP 43.40 grams PAA-3 74,000 Manufacturing Example 4 10.11 grams (25 millimoles) 5.31 grams (25 millimoles) DMAc 70 grams PAA-4 41,000 Examples 1 to 3: To 10 g of each of the polyfluorene imide precursor solutions (any of PAA-1 to PAA-3) prepared in Production Examples 1 to 3 was added 027 g of 2 6-fluorene (4, _ azido Benzaldehyde) winter carboxycyclohexyl ig (CA), 0.027 g 4,4, -fluorene (diethylamino) benzophenone (EBA) and 0.054 g 1-phenyl-2- (o-ethoxycarbonyl) ) Propylpropan-1-one (PDO). Then add dimethylaminopropyl methacrylate (MDAP), the amount of MDAP added is the equivalent of the carboxyl equivalent of the polyimide precursor. Mix with stirring Get the sensitivity of Examples 1 to 3 Homogeneous solution of resin composition. Example 4: (Please read the precautions on the back before filling out this page) Packing -------- Order --------- Line 1 Ministry of Economy Intellectual Property Bureau Staff Consumption Cooperative printed 2.50 grams of Polyimide Precursor (PAA-4) prepared in Manufacturing Example 4 The paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) 33 311836 1225969 A7 B7 V. Invention Note (34) (Please read the note on the back? Matters and then fill out this page) Solution 5.83 g of γ-butyrolactone, add 0.027 g of 2,6-jia (4, -azidobenzaldehyde) ) · 4-Carboxycyclohexanone (CA), 0.027 g of 4,4, -fluorene (diethylamino), a benzyl ether (ΕΒΑ) and 0.054 g of 1-phenyl-2 · (o-ethoxy) A few bases) sylpropan-1-one (PDO). Stir and mix to obtain a homogeneous solution of the photosensitive resin composition of Example 4. The photosensitive resin composition solution prepared as above was separated by filtration. Each was applied dropwise by spin coating to On a silicon wafer, and then heated and dried on a 1000 hot plate for 150 seconds to form a 15 micron film on the wafer. The i-line stepper 'film was exposed through a patterned mask at 100 ° C was heated for 60 seconds, and then developed using a paddle with an N-methyl-2-Π ratio of pyrrolidone / water (75/25 weight ratio). The polyimide resin pattern was obtained by further heating at 100 ° C for 30 minutes, 200 ° C for 30 minutes, and 3 50 ° C for 60 minutes. The transmittances of the polyimide precursors (PAA-1 to PA A-4) prepared in Manufacturing Examples 1 to 4, and the thermal expansion coefficient of the polyimide film made of the precursors' Polyimide on a silicon wafer The residual stress of the amine film and the resolution of the polyimide stress relief pattern were measured and evaluated according to the following methods. The information is shown in Table 2. The measurement of the transmittance is printed as follows by the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs: the resin solution of each polyimide precursor (PAA-1 to PAA_ 4) is spin-coated on the substrate and dried at 85 ° c. Minutes, then dried at 105 ° C for 3 minutes. The transmittance of the obtained film (thickness · 10 µm) was measured using a spectrophotometer. The thermal expansion coefficient is measured as follows: Polyimide film with a thickness of 10 microns is formed by applying each polyimide precursor (PAA-1 to PAA-4) resin solution on the substrate and then heating and drying. The film is based on 10 10 g under load. (: / Min rate heating, and the paper size measured by TMA is applicable to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 34 311836 1225969 A7 B7 V. Description of the invention (35) Thermal expansion coefficient. Residual stress measurement As follows: Polyimide films are formed from various photosensitive resin compositions on a 6-inch silicon wafer. The residual stress is measured at 25 ° C using a thin film stress meter (Tanker FLX-2320 model). For the resolution of the resin composition, the through-hole pattern is formed by each composition. The minimum size of the formed through-hole that can be developed indicates the resolution of the resin composition to be tested. Table 2 i of the polyimide precursor precursor Linear transmittance (%) Example Example 2 Example Example 4 Residual stress of polyimide thin film (million bska) Resolution in micrometers (please read the note on the back? Matters before filling this page) PAA-1 PAA -2 PAA-3 PAA-4 41 53 51 12 8 12 14 micrometers 5 micrometers 6 micrometers 6 micrometers Intellectual Property Bureau of the Ministry of Economic Affairs Employee Cooperatives Printing Examples 5 and 6, f Examples 9 and 10: (1) Radon solution Preparation: Table 3 of 0.03 Molar Acid anhydride, 7.81 g (0.06 mol) of methyl 2-hydroxyethyl acrylate (HEMA), 4.75 g (0.06 mol) of mouth-to-mouth bite, 0.001 g of Fentonium and 70 ml of N, N-dimethylacetamide (DMAc) was placed in a 200-milliliter: four-necked flask, and stirred at 60 ° C for 2 hours to obtain a transparent solution. The solution was added to the mixture for 7 hours. Next, the flask was cooled with ice, $ 7 g (q 〇07 mol) of sulfen gas is added dropwise over a period of 10 minutes. This mixture is further stirred at room temperature for 1 hour to obtain a solution containing gas. (2) Polyimide precursor Manufacture: 0 03 Molar of the diamine shown in Table 3, 5.06 g (0064 Molar) roar and bite '0.01 g of hydroquinone and 50 ml of DMAc in another 200 ml of Mai

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, 1225969 V. Description of the invention (in a 36 颏 bottle. The mixture in the bottle is cooled with ice (cooled to no higher than 〖0 ... temperature), and (1) the radon gas prepared The solution was added dropwise over 1 hour. Then the mixture was further stirred at room temperature for i hours and poured into i liters of water. The polymer thus precipitated was removed by filtration, washed twice and dehydrated in vacuo. The resulting polymer powder was dissolved in γ -Butyrolactone (γ-BL) obtains a controlled viscosity of 80 poises. In this way, a polyfluorene imide precursor solution (PAEq, 2, ρΑΕ_5, 6b, Manufacturing Example 7 and S: (1) Preparation of a tritium gas solution : 0.03 Molar of the acid anhydride shown in Table 3, 006 Molar n-butanol, 475 g (0.06 Molar) of pyridine and 70 ml of dimethylacetamide (dmAc) in 200 ml of four Inside the flask, stir at 60t for 2 hours to obtain a transparent solution. Stir at room temperature for 7 hours. Next, the flask was cooled with ice, and 857 g (0.072 mol) of sulfinic acid was added dropwise over 10 minutes. To this, it was further stirred at room temperature for 1 hour to obtain radon-containing gas. (2) Manufacturing of polyimide precursors: One 0.03 mole of the diamine shown in Table 3, 5.06 g (0.064 mole) of pipiridine and 50 ml of DMAc were placed in another 200. In a four-necked milliliter flask. When the mixture in the flask is cooled with ice (cooled to a temperature not higher than 10t) and stirred, (1) the radon solution prepared is added dropwise to it over 1 hour. Then the mixture is further processed in Stir at room temperature for 1 hour, then pour into 1 liter of water. The polymer in Shen Dian was then taken out by filtration, washed twice and dehydrated under vacuum. The obtained polymer powder was dissolved in γ-butyrolactone (γ-BL) to obtain a controlled viscosity. 80 poises. In this way, a polyimide precursor solution (ραε_3, 4) was prepared. The viscosity was measured with an E-type viscometer (EHD model from Toki Industry Co., Ltd.). ----- Order --------- Line l · (Please read the precautions on the back before filling this page} This paper size applies to China National Standard (CNS) A4 (210 χ 297 mm) 36 311836 1225969 A7 B7 V. Description of the invention (38) Liquid development. Further heating at 350 ° C for 60 minutes to obtain polyimide resin pattern. (Please read first Note on the back? Please fill in this page again.) Part of the polyimide stress relief pattern was tested by potassium bromide_infrared spectroscopy, and specific imidate absorption was obtained at about 1780 cm-1. Manufacturing Examples 5 to 1 〇 The light transmittance of the prepared polyimide precursors (pAE) to pAE_6, the residual stress of the polyimide film on the silicon wafer, and the resolution of the polyimide stress relief pattern were measured according to the following methods and The information is shown in Table 4. The transmittance was measured as follows: a resin solution of each of the polyimide precursors (PAE-1 to PAE-6) was applied to the substrate by spin coating, and dried at 85 ° C for 2 minutes and then Dry at 105 ° C for 2 minutes. The transmittance of the obtained film (thickness: 10 micrometers) was measured using spectrophotometry. Residual stress was measured as follows: On a 5-inch silicon wafer, a polyimide film with a thickness of 10 microns was formed from various photosensitive resin compositions. The residual stress was measured using a thin film stress meter (Tanker FLX-2320 model) Measure. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. To measure the resolution of the photosensitive resin composition, a through-hole test pattern is formed from each composition. The minimum size of the visible through-hole formed indicates the resolution of the resin composition to be tested. The stress relief patterns formed in Examples 5 to 8 and Comparative Examples 1 and 2 were heated at 350 ° C for 60 minutes under a nitrogen atmosphere to obtain polyimide patterns. The polyimide patterns obtained from the stress relief patterns of Examples 5 to 8 had good trapezoidal side views in cross section and reflected the good rectangular side views of the original stress relief pattern with high resolution. However, the cross-section of the polyimide pattern obtained from the stress relief patterns of Comparative Examples 1 and 2 is an unfavorable inverted trapezoidal side view, which reflects that this paper scale is applicable to the Chinese National Standard (CNS) A4 specification (21 × 297 mm). (%) 38 311836 1225969 A7 _B7 V. Description of the invention (39) The disadvantageous inverted trapezoidal side view of the original stress relief pattern has low resolution. Table 3 Weight average molecular weight (Mw) of acid component diamine component polyfluorene imide precursor Production Example 5 MTXDA DDE-A PAE-1 41000 Production Example 6 SIXDA DDE-A PAE-2 33000 Production Example 7 MMXDA 2,2-HAB PAE-3 27000 Manufacturing Example 8 6FCDA 3,3-HAB PAE-4 30000 Manufacturing Example 9 s-BPDA DDE-A PAE-5 36000 Manufacturing Example 10 PMDA DDE-A PAE-6 32000 MTXDA:

(Please read the notes on the back before filling this page) SIXDA:

MMXDA: Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 6FCDA:

O s-BPDA: Biphenyltetracarboxylic dianhydride The paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) 39 311836 1225969 A7 B7 V. Description of the invention (4〇) PMDA Acid two needle DDE-A:

2,2 · ΗΑΒ:

3,3-ΗΑΒ:

(Please read the precautions on the back before filling this page) Table 4 i-line transmittance of the precursor (° / 〇) Example 5 50 tm 6 35 Example 7 — One 20 Example 8 15 [Comparative example 1 20 ^ 2 — — 0.1 1 Residual stress (million basca) Printed resolution (micron) by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The present invention can solve the problems that were not solved by the prior art by providing the aforementioned excellent photosensitive resin composition. In particular, the aromatic polyfluorene imide precursor of the composition of the present invention has a high i-ray transmittance, and the polyfluorene imine resin derived from the precursor through the fluorene imidization reaction has low stress. In addition, the precursor film has the advantages of good heat resistance, high sensitivity, and high resolution. The photosensitive resin composition of the present invention can be developed using an aqueous alkali solution that has no effect on the environment. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

Optional external amendment Η3 Ⅱ-Patent No. 89119305 Patent Application Amendment to Patent Scope (September 24, 1993) 1_ A photosensitive resin composition 'comprising an aromatic polyimide precursor and photopolymerization initiation When the composition is a negative photosensitive composition, or a compound capable of generating an acid in light, when the composition is a positive photosensitive composition, the precursor layer having a thickness of 10 microns has a thickness of 365 millimeters. A light transmittance of at least 1% in micrometers, and a polyimide film of 10 micrometers in thickness made of a polyimide composition and deposited on a silicon substrate via a closed loop of the imidized ring can obtain a residual stress of up to 25 Million Baska, wherein the aromatic polyfluorene imide precursor has the structural unit of the general formula (Γ): Qi / Q2. Ql / (^ QdQ2 Q1 and Q2 each represent hydrogen or a lower alkyl group, and the lower alkyl group may be substituted by an i atom; and X represents C or Si. Printed by the Staff Welfare Committee of the Central Bureau of Standards of the Ministry of Economic Affairs 2. If the photosensitive resin composition of the first scope of the patent application, the light transmittance at a wavelength of 365 nm is at least 5%. 3. The photosensitive resin composition according to item 1 of the application, wherein the aromatic polyimide precursor is soluble in an aqueous test solution. 4. The photosensitive resin composition according to item 1 of the patent application scope, wherein the photosensitive resin composition is a negative photosensitive resin composition. 5. If the photosensitive resin composition of item 1 in the patent application scope, the sense 1 (revised version) 311836 This paper size is applicable to China National Standard (CNS) A4 specification (210X297) Chu 1225969 H3 The photosensitive resin composition is Positive type photosensitive resin composition. 6. A photosensitive resin composition comprising an aromatic polyimide precursor, wherein the aromatic polyimide precursor has a structural unit of the general formula (I,): Q1 and Q2 each represent hydrogen or a C! _6 lower alkyl group, and the lower alkyl group may be substituted by a # atom; and X represents C or Si. 7. The photosensitive resin composition according to item 6 of the application, wherein the aromatic polyfluorene imine precursor having the structural formula of the formula (I) has a repeating structural unit of the general formula (Π): Printed by the Staff Welfare Committee of the Central Bureau of Standards, Ministry of Economic Affairs, where Q and Q2 represent hydrogen or Cl_6 lower alkyl group, respectively, and the lower alkyl group may be replaced by a halogen atom; X represents C or si; R1 and R2 each represent hydroxyl or monovalent Organic group; Z represents a divalent aromatic group. 8- The photosensitive resin composition according to item 7 of the scope of patent application, wherein R1 or R2 of the formula (π) is a monovalent organic group containing a photosensitive group. 9. If the photosensitive resin composition of item 8 of the patent application scope, wherein R1 or R2 of the formula (π) is the base of the following formula: -〇n + hr4r5-r6 -〇-R6 or this paper size applies Chinese national standards ( CNS) A4 specification (210X297 mm) 2 (Revised version) 311836 1225969 -NH-R6 In the formula, R4 and R5 are each i-L branch, and the mesh is not a hydrocarbon group, and R6 represents a monovalent organic group. For example, the photosensitive resin composition of claim 9 of the patent scope, wherein V is a group containing a carbon-carbon unsaturated double bond. 〃 For example, the photosensitive resin composition in the ninth scope of the patent application, wherein R1 or R2 of formula 为 is the following formula ... -ctn + hr4r5-r6 where R4 and R5 each represent a hydrocarbon group, and R6 represents a carbon content. Carbon unsaturated double bond is a monovalent organic group. 12. The photosensitive resin composition according to item 7 of the scope of patent application, wherein R1 or R2 of the formula (ιι) is: a -0_R6 group, where 'R represents a monovalent organic group. 13. The photosensitive resin composition according to the scope of the patent application, wherein the aromatic polyimide precursor is soluble in an aqueous test solution. Printed by the Staff Welfare Committee of the Central Bureau of Standards of the Ministry of Economic Affairs. 14. If the photosensitive resin composition of the scope of patent application No. 13 is used, Z in the formula (II) is a group containing a carboxyl group or a phenolic hydroxyl group. 15. For example, the photosensitive resin composition of the scope of application for patent No. 14, wherein Z of the formula (II) is a group of the general formula (in): R1 R1 (III) 3 (revised version) 311836 This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 1225969 where z 'represents a single bond, ch, ch2, s or S02; R11 to R1; Each represents h, COOH, oh, an alkyl group containing from 1 to 10 carbon atoms: a fluorine radical containing 1 to 10 carbon atoms, a fluoroalkoxy group or a tooth atom containing ^ 10 carbon atoms, And wherein at least one of the Rlls Rls is COOH or OH. 16. The photosensitive resin composition according to any one of item a 15 of the patent application park, which further contains a photopolymerization initiator and has negative photosensitive characteristics. 17. The photosensitive resin composition as described in any one of items 6 to 15 in the patent scope of Shenyan, which further contains a compound capable of generating an acid in light, and has a positive photosensitive property. 18 · —A photosensitive resin composition comprising an aromatic polyfluorene imine precursor, wherein the resin composition is prepared by a polyimide ring closure reaction and is deposited on a stone evening substrate with a thickness of 10 micrometers. Imine film with a light transmittance of at least 1% at a wavelength of 365 nanometers and a residual stress of at most 25 million Baska 'wherein the aromatic polyfluorene imide precursor includes the formula (Γ) repeating unit: Central Ministry of Economic Affairs Printed by Standards Bureau Staff Welfare Committee Or Q: xQ2 (I, where Q1 and Q2 represent hydrogen or Cl_6 lower alkyl group, respectively, the lower alkyl group may be substituted by a tooth atom; and X represents C or Si. 19. A method for forming a pattern, comprising applying a photosensitive resin The composition is dried on the substrate and the composition is exposed to light, the composition is developed, and the paper is heated on the paper scale @ 家 标 格 （210χ29ϋ 4 (revised version) 311836 1225969 H3 The composition 'wherein the composition Containing a photosensitive resin composition, including an aromatic polyfluorene imine precursor 'wherein the resin composition is prepared by a fluorinated ring closure reaction and is deposited on a Shixi substrate with a thickness of 10 micrometers of polyfluorene imide precursor Thin film with a light transmittance of at least 1% at a wavelength of 365 nanometers and a residual stress of at most 25 million Baska, and the aromatic polyfluorene imide precursor has a structural unit of the general formula (Γ): Or V2 (I) Printed by the Staff Welfare Committee of the Central Standards Bureau of the Ministry of Economics, where Q1 and Q2 represent hydrogen or Cu lower alkyl, respectively, and the lower alkyl group may be replaced by a drawing atom; and X represents C or Si. 20. The method according to item 19 of the patent application, wherein the line is used as the light source in the exposure step. 21 · The method according to item 19 or 20 of the patent application scope, wherein the substrate is a silicon wafer having a diameter of at least 12 inches. 22 · —An electronic component having a patterned layer according to the method of claim 19 of the scope of patent application. 23. The electronic component as claimed in claim 22, wherein the component is a semiconductor device, and the patterned layer is a surface protective film. 24. The electronic component of claim 22, wherein the patterned layer is an interlayer insulating film. A4 specifications (210X297 mm)